Role of dipolar and exchange interactions in the positions and widths of EPR transitions for the single-molecule magnets Fe8 and Mn12

We examine quantitatively the temperature dependence of the linewidths and line shifts in electron paramagnetic resonance experiments on single crystals of the single-molecule magnets Fe$_8$ and Mn$_{12}$, at fixed frequency, with an applied magnetic field along the easy axis. We include inter-molecular spin-spin interactions (dipolar and exchange) and distributions in both the uniaxial anisotropy parameter $D$ and the Land\'{e} $g$-factor. The temperature dependence of the linewidths and the line shifts are mainly caused by the spin-spin interactions. For Fe$_8$ and Mn$_{12}$, the temperature dependence of the calculated line shifts and linewidths agrees well with the trends of the experimental data. The linewidths for Fe$_8$ reveal a stronger temperature dependence than those for Mn$_{12}$, because for Mn$_{12}$ a much wider distribution in $D$ overshadows the temperature dependence of the spin-spin interactions. For Fe$_8$, the line-shift analysis suggests two competing interactions: a weak ferromagnetic exchange coupling between neighboring molecules and a longer-ranged dipolar interaction. This result could have implications for ordering in Fe$_8$ at low temperatures.Comment: published versio

Nuclear spin-lattice relaxation in ferrimagnetic clusters and chains: A contrast between zero and one dimensions

Motivated by ferrimagnetic oligonuclear and chain compounds synthesized by Caneschi et al., both of which consist of alternating manganese(II) ions and nitronyl-nitroxide radicals, we calculate the nuclear spin-lattice relaxation rate 1/T_1 employing a recently developed modified spin-wave theory. 1/T_1 as a function of temperature drastically varies with the location of probe nuclei in both clusters and chains, though the relaxation time scale is much larger in zero dimension than in one dimension. 1/T_1 as a function of an applied field in long chains forms a striking contrast to that in finite clusters, diverging with decreasing field like inverse square root at low temperatures and logarithmically at high temperatures.Comment: to be published in Phys. Rev. B 68 August 01 (2003

Magnetic Field Effects on the Far-Infrared Absorption in Mn_12-acetate

We report the far-infrared spectra of the molecular nanomagnet Mn_12-acetate (Mn_12) as a function of temperature (5-300 K) and magnetic field (0-17 T). The large number of observed vibrational modes is related to the low symmetry of the molecule, and they are grouped together in clusters. Analysis of the mode character based on molecular dynamics simulations and model compound studies shows that all vibrations are complex; motion from a majority of atoms in the molecule contribute to most modes. Three features involving intramolecular vibrations of the Mn_12 molecule centered at 284, 306 and 409 cm-1 show changes with applied magnetic field. The structure near 284 cm$^{-1}$ displays the largest deviation with field and is mainly intensity related. A comparison between the temperature dependent absorption difference spectra, the gradual low-temperature cluster framework distortion as assessed by neutron diffraction data, and field dependent absorption difference spectra suggests that this mode may involve Mn motion in the crown.Comment: 5 pages, 4 figures, PRB accepte

Detailed single crystal EPR lineshape measurements for the single molecule magnets Fe8Br and Mn12-ac

It is shown that our multi-high-frequency (40-200 GHz) resonant cavity technique yields distortion-free high field EPR spectra for single crystal samples of the uniaxial and biaxial spin S = 10 single molecule magnets (SMMs) [Mn12O12(CH3COO)16(H2O)4].2CH3COOH.4H2O and [Fe8O2(OH)12(tacn)6]Br8.9H2O. The observed lineshapes exhibit a pronounced dependence on temperature, magnetic field, and the spin quantum numbers (Ms values) associated with the levels involved in the transitions. Measurements at many frequencies allow us to separate various contributions to the EPR linewidths, including significant D-strain, g-strain and broadening due to the random dipolar fields of neighboring molecules. We also identify asymmetry in some of the EPR lineshapes for Fe8, and a previously unobserved fine structure to some of the EPR lines for both the Fe8 and Mn12 systems. These findings prove relevant to the mechanism of quantum tunneling of magnetization in these SMMs.Comment: Phys. Rev. B, accepted with minor revision

Deuteron NMR of a manganese-ion cluster nanomagnet

The temperature dependence of deuteron NMR spectra of the fully deuterated manganese ion cluster nanomagnet $\rm Mn_{12}O_{12}$-acetate has been measured. Two sets of deuteron peaks have been observed which both shift towards lower fields with decreasing temperature. The strongly shifted peak is associated with the deuterons of the four $\rm D_2O$ molecules which are directly attached to the Mn core. The less shifted peak is due to the $-\rm CD_3$ deuterons, which are three bonds away from the oxygen that is attached to Mn ions, as well as to the solvated $\rm D_2O$ and $\rm CD_3COOD$ molecules. The results imply that the unpaired spin density extends over the whole molecular cluster rather than being concentrated at the Mn ions